Formation of Carbon-Carbon Bonds by Oxidative-Addition Reactions to trans-MeIr(CO)(P(p-tolyl)3)2

Jeffrey S. Thompson; Jim D. Atwood

doi:10.1021/om00056a023

Formation of Carbon-Carbon Bonds by Oxidative-Addition Reactions to trans-MeIr(CO)(P(p-tolyl)₃)₂

Jeffrey S. Thompson
, Jim D. Atwood

Chemistry

SUNY Buffalo

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

Oxidative addition of various organic halides to trans-Ir(CO)(Me)(P(p-tolyl)₃)₂ has been examined by variable-temperature NMR spectroscopy. For PhCH₂Cl, CH₃C(O)C1, Ph₂CHC(O)Cl, PhC(O)Cl, and PhCH₂C(O)Cl oxidative addition is followed by reductive elimination to form carbon-carbon bonds. For reaction of trans-Ir(CO)(Me)(P(p-tolyl)₃)₂ with CH₃C(O)Cl the intermediate is characterized by ¹H and ³¹P NMR spectroscopy at −5°; acetone elimination is significant at 10 °C. For the other complexes the oxidative addition is sufficiently slow that an intermediate cannot be identified. Oxidative addition of Mel and EtI to trans-MeIr(CO)(P(p-tolyl)₃)₂ leads to complexes Ir(CO)(I)(R)(Me)(P(p-tolyl)₃)₂ that are characterized by ¹H and ³¹P NMR spectroscopy. For R = Me this complex is stable; for R = Et the complex slowly undergoes β-elimination leading to C₂H₄ and CH₄. These results provide strong support for a mechanism involving halide dissociation from the iridium(III) complexes.

Original language	English
Pages (from-to)	3525-3529
Number of pages	5
Journal	Organometallics
Volume	10
Issue number	10
DOIs	https://doi.org/10.1021/om00056a023
State	Published - Oct 1 1991

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title = "Formation of Carbon-Carbon Bonds by Oxidative-Addition Reactions to trans-MeIr(CO)(P(p-tolyl)3)2",

abstract = "Oxidative addition of various organic halides to trans-Ir(CO)(Me)(P(p-tolyl)3)2 has been examined by variable-temperature NMR spectroscopy. For PhCH2Cl, CH3C(O)C1, Ph2CHC(O)Cl, PhC(O)Cl, and PhCH2C(O)Cl oxidative addition is followed by reductive elimination to form carbon-carbon bonds. For reaction of trans-Ir(CO)(Me)(P(p-tolyl)3)2 with CH3C(O)Cl the intermediate is characterized by 1H and 31P NMR spectroscopy at −5°; acetone elimination is significant at 10 °C. For the other complexes the oxidative addition is sufficiently slow that an intermediate cannot be identified. Oxidative addition of Mel and EtI to trans-MeIr(CO)(P(p-tolyl)3)2 leads to complexes Ir(CO)(I)(R)(Me)(P(p-tolyl)3)2 that are characterized by 1H and 31P NMR spectroscopy. For R = Me this complex is stable; for R = Et the complex slowly undergoes β-elimination leading to C2H4 and CH4. These results provide strong support for a mechanism involving halide dissociation from the iridium(III) complexes.",

author = "Thompson, \{Jeffrey S.\} and Atwood, \{Jim D.\}",

year = "1991",

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doi = "10.1021/om00056a023",

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T1 - Formation of Carbon-Carbon Bonds by Oxidative-Addition Reactions to trans-MeIr(CO)(P(p-tolyl)3)2

AU - Thompson, Jeffrey S.

AU - Atwood, Jim D.

PY - 1991/10/1

Y1 - 1991/10/1

N2 - Oxidative addition of various organic halides to trans-Ir(CO)(Me)(P(p-tolyl)3)2 has been examined by variable-temperature NMR spectroscopy. For PhCH2Cl, CH3C(O)C1, Ph2CHC(O)Cl, PhC(O)Cl, and PhCH2C(O)Cl oxidative addition is followed by reductive elimination to form carbon-carbon bonds. For reaction of trans-Ir(CO)(Me)(P(p-tolyl)3)2 with CH3C(O)Cl the intermediate is characterized by 1H and 31P NMR spectroscopy at −5°; acetone elimination is significant at 10 °C. For the other complexes the oxidative addition is sufficiently slow that an intermediate cannot be identified. Oxidative addition of Mel and EtI to trans-MeIr(CO)(P(p-tolyl)3)2 leads to complexes Ir(CO)(I)(R)(Me)(P(p-tolyl)3)2 that are characterized by 1H and 31P NMR spectroscopy. For R = Me this complex is stable; for R = Et the complex slowly undergoes β-elimination leading to C2H4 and CH4. These results provide strong support for a mechanism involving halide dissociation from the iridium(III) complexes.

AB - Oxidative addition of various organic halides to trans-Ir(CO)(Me)(P(p-tolyl)3)2 has been examined by variable-temperature NMR spectroscopy. For PhCH2Cl, CH3C(O)C1, Ph2CHC(O)Cl, PhC(O)Cl, and PhCH2C(O)Cl oxidative addition is followed by reductive elimination to form carbon-carbon bonds. For reaction of trans-Ir(CO)(Me)(P(p-tolyl)3)2 with CH3C(O)Cl the intermediate is characterized by 1H and 31P NMR spectroscopy at −5°; acetone elimination is significant at 10 °C. For the other complexes the oxidative addition is sufficiently slow that an intermediate cannot be identified. Oxidative addition of Mel and EtI to trans-MeIr(CO)(P(p-tolyl)3)2 leads to complexes Ir(CO)(I)(R)(Me)(P(p-tolyl)3)2 that are characterized by 1H and 31P NMR spectroscopy. For R = Me this complex is stable; for R = Et the complex slowly undergoes β-elimination leading to C2H4 and CH4. These results provide strong support for a mechanism involving halide dissociation from the iridium(III) complexes.

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U2 - 10.1021/om00056a023

DO - 10.1021/om00056a023

M3 - Article

AN - SCOPUS:0039761164

SN - 0276-7333

VL - 10

SP - 3525

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JO - Organometallics

JF - Organometallics

IS - 10

ER -

Formation of Carbon-Carbon Bonds by Oxidative-Addition Reactions to trans-MeIr(CO)(P(p-tolyl)₃)₂

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